Bis-tris propane as a flexible ligand for high-nuclearity complexes
Bis-tris propane as a flexible ligand for high-nuclearity complexes
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DOI：
10.1016/j.poly.2018.04.038
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发表时间：
2018-08
期刊：
影响因子：
2.6
通讯作者：
M. Murrie
中科院分区：
文献类型：
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作者：
M. Murrie
多金属配合物可以使用多种多齿配体进行组装，这些配体提供了几乎无限的工具箱来制备具有迷人结构和有趣磁性的新分子结构。 Bis-tris丙烷就是这样一种多齿配体，已用于制备同质（3d或4f）和异金属（3d/3d'或3d/4f）配合物，范围从简单的配合物（例如{Ni4}）到壮观的3d/3d'{Cu8Zn8}或{Mn18Cu6}配合物。它显示出结合模式的灵活性，利用多达六个潜在配体供体原子并显示出多个水平的去质子化，能够桥接多达六个金属离子。该配体在异金属合成中对结合 3d 离子（例如 Cu(II) 或 Co(III)）具有特殊的亲和力，这可以提供灵活的结构导向效应。这一概念已被用来制备新的异金属 3d/3d' 配合物，这些配合物显示出有趣的复杂程度； 3d/4f 复合物，例如显示单分子磁体行为的 {Cu3Tb2}，其中超交换相互作用淬灭磁化的量子隧道效应，或 {Co3Gd3}，其中通过使用 Bis-tris 丙烷分离 Gd(III) 离子并减弱 Gd(III)…Gd(III) 相互作用而产生磁热特性。
Polymetallic complexes can be assembled using a wide array of polydentate ligands that give an almost unlimited toolbox to prepare new molecular architectures with fascinating structures and interesting magnetic properties. Bis-tris propane is one such a polydentate ligand that has been used to prepare homo- (3d or 4f) and heterometallic (3d/3d′ or 3d/4f) complexes, ranging from simple complexes such as {Ni4} to spectacular 3d/3d′ {Cu8Zn8} or {Mn18Cu6} complexes. It shows a flexibility in binding mode, utilizing up to six of its potential ligand donor atoms and displaying multiple levels of deprotonation, able to bridge up to six metal ions. The ligand has a particular affinity for binding 3d ions such as Cu(II) or Co(III) in heterometallic syntheses and this can provide a flexible structure-directing effect. This concept has been exploited to prepare new heterometallic 3d/3d′ complexes that display interesting levels of complexity; 3d/4f complexes such as {Cu3Tb2} that show single-molecule magnet behavior where superexchange interactions quench quantum tunneling of the magnetization, or {Co3Gd3} where the magnetocaloric properties arise by using Bis-tris propane to separate the Gd(III) ions and weaken Gd(III)…Gd(III) interactions.